Nickel catalysts for oxidative coupling of phenols

ABSTRACT

Carbon-to-carbon coupled self-condensation products are obtained by the oxidative coupling of substituted phenols in the presence of a heterogeneous dehydrogenation catalyst comprising nickel.

BACKGROUND OF THE INVENTION

The invention relates to an improved method of producing binary selfcondensation products of phenols. It is well-known in the art thatsubstituted phenols can be oxidized to yield self-condensation products,especially diphenoquinones and biphenols. The diphenoquinones are usefulantioxidants. Biphenols are useful antioxidants, stabilizers andintermediates for the synthesis of various polymers, especiallypolyesters.

In U.S. Pat. No. 4,195,189, a one-step process for the oxidativecoupling of phenols is described wherein molten phenols are combinedwith an oxidizing agent which is activated copper oxide. The copperoxide was employed in about equal or greater molar ratio with thephenolic compound. In this process the copper oxide is employed not as acatalyst but as a source of oxygen as no oxygen or oxygen-containing gasis otherwise present during the reaction.

In German Pat. No. 536,277, the oxides of copper, manganese and leadwere employed in the oxidative reaction of phenol. The reaction product,however, was most probably a polymeric material as it was described as alight grey amorphous precipitate without a sharp melting point whichsintered to a brown mass at 120° C. to 130° C. Diphenoquinone is ahighly colored crystalline material which melts at about 165° C.

SUMMARY OF THE INVENTION

The present invention comprises an improved process for thecarbon-carbon oxidative coupling of phenols. Accordingly,diphenoquinones and biphenols are prepared by carbon-carbon coupling inaccordance with the following general reactions depending on thereactive sites available in the phenol employed. ##STR1## Each R iseither hydrogen, halogen or R₁, and each R₁ is a substituent having upto 10 carbons selected from hydrocarbon, halohydrocarbon orhydrocarbonoxy. Preferred phenol reactants are 2,6-disubstituted phenolswhich couple to form 3,3',5,5'-tetrasubstituted-p,p'-diphenoquinones.Most preferred are 2,6-dialkyl-substituted phenols. The phenol reactantsare contacted in the presence of oxygen or an oxygen-containing gas witha heterogeneous dehydrogenation catalyst comprising nickel. The reactionis preferably conducted at elevated temperatures and pressures. Thediphenoquinone reaction products were produced may be reduced by knownmethods, for example, by contact with a heterogeneous hydrogenationcatalyst to produce the corresponding biphenol if desired. Also, ifdesired, where R is hydrogen and each R₁ is an alkyl group that iseasily removable, the substituted biphenol may be dealkylated accordingto the invention to produce an unsubstituted biphenol. Suitable easilyremovable alkyl groups include tertiary butyl or tertiary amyl.

DETAILED DESCRIPTION OF THE INVENTION

The substituted phenol reactants here used are those well-known in theart as forming oxidative carbon-to-carbon coupling products. Examplesare 2,6-dimethyl phenol, 2,6-diethyl phenol, 2,6-ditertiary butylphenol, 2,6-diisobutyl phenol, 2-octyl-6-methyl phenol,2,6-ditertiary-hexyl phenol, 2-ethyl-6-methyl phenol,2-methyl-6-tertiary butyl phenol, 2-cyclohexyl-6-methyl phenol,2,6-dimethoxy phenol, 2,6-dibutoxy phenol, 2-methoxy-3-ethoxy-6-methylphenol, 2,4-dimethyl phenol, 2,4-ditertiary butyl phenol,2-methyl-4-amyl phenol, 2-methyl-4-ethoxy phenol, 2-ethoxy-3,4-dimethylphenol, 2,4-dimethyl-3,5-dichlorophenol, etc. Because of sterichinderance, when the 2,4-substituted phenolic compounds are coupled inthe ortho position, the substituent on the 3-position is preferablyhydrogen, halogen or a short-chain alkyl group. Generally like phenolcompounds are coupled to reduce the variety of reaction products formed,unless of course a mixture of products is acceptable. As previouslymentioned, the preferred phenolic reactant is 2,6-ditertiary butylphenol.

The oxygen used is either oxygen itself or an oxygen-containing gas suchas air. While any suitable pressure from atmospheric to elevatedpressures may be employed, it is preferred, in order to produce improvedreaction rates and yields, to employ elevated pressures. The reaction isnormally conducted in a pressurized system with the oxygen-containinggas supplying the pressurizing means. Elevated pressures of up to about500 psig may be employed depending on the amount of oxygen present inthe gas mixture and the pressure vessel design limits. Utilizing air asthe oxidizing medium pressures of about 100-450 psig are suitable.

The reaction is conducted at elevated temperatures of from about 30° C.to about 200° C., preferably from about 50° C. to about 150° C. and mostpreferably from about 60° C. to about 100° C. for the time necessary toform substantial amounts of the desired tetra-substituteddiphenoquinone.

The process may be operated without a solvent, interchangeably referredto herein as a liquid reaction medium, in which case the substitutedphenol itself acts as a solvent. However, preferably a liquid reactionmedium is employed in order to aid in transport of reactants and inrecovery of the products. Any liquid under the reaction conditions thatis relatively unreactive is acceptable. The reactants and products neednot be highly soluble therein and indeed may be insoluble. Examplesinclude such organic liquids as lower carboxylic acids, alcohols, andaromatic compounds. Preferred solvents may differ depending on thenature of the phenol reactant, the catalyst and the reaction conditionsemployed. Particularly, preferred liquids are polar compounds,particularly lower alcohols which are not themselves easily oxidizable.An example is methanol.

The catalysts employed are heterogeneous dehydrogenation catalystscomprising nickel as the active catalytic species. The catalysts arewell-known and may be purchased commercially. Generally,nickel-containing catalysts are provided as surface coatings of nickeloxide on an inert substrate such as carbon, silica, alumina,diatomaceous earth, clays, etc. Such substrates are employed to provideincreased surface area for the catalyst. The nickel oxide may be presentin amounts from about 1 percent up to about 70 percent or higher.

In the operation of the invention, the heterogeneous dehydrogenationcatalyst is placed into a suitably designed reactor vessel fitted with areactant inlet and product outlet along with heating means as well as anentrance and exit means for the oxygen-containing gas. Initially, thecatalyst may be added in either a reduced or a highly oxidized stateinasmuch as under the instant process conditions, the catalyst acquiresthe correct oxidation state to result in formation of carbon-carbonoxidatively coupled reaction products.

The reactor vessel is next charged with a solution of a substitutedphenol in the previously described liquid reaction medium. In a batchoperation, the reactor is then sealed and heated to the desired reactiontemperatures accompanied by oxygen addition. Agitation, as for exampleby stirring, may also be employed. In a continuous operation, thereactant charge is supplied to a reactor containing the catalyst that ismaintained at the desired temperature. A stream of oxygen-containing gasis also suppled to the reactor either concurrently or countercurrentlyand the product mixture is continuously removed.

The substituted diphenoquinone in the product mixture is separated fromunreacted substituted phenol if necessary and may even be separated fromthe liquid reaction medium as by distillation or precipitation.Preferably, however, the crude mixture containing substituteddiphenoquinone is further charged to a second reactor containing aheterogeneous hydrogenation catalyst maintained under reducingconditions. Suitable hydrogenation catalysts are those heterogeneoushydrogenation catalysts previously known in the art, such as the noblemetals, nickel, copper chromite, etc. The reaction conditions employedare substantially modified from the oxidative coupling conditionsinitially employed in order to effect the desired hydrogenation.Generally, the hydrogenation is conducted at temperatures from about 25°C. to about 150° C. and pressures from about atmospheric to about 100psig in the presence of a hydrogen-containing gas.

Alternatively, the reduction may be accomplished by reacting thediphenoquinone with additional phenol, or unreacted phenol from theoxidative coupling reaction in the presence of base at an elevatedtemperature as is previously known in the art and taught, for example,in U.S. Pat. No. 3,562,338 which teaching is incorporated herein byreference.

The hydrogenation product is the corresponding substituted biphenolwhich may be recovered from the reaction mixture. As previouslymentioned, in a preferred phenol reactant, each R₁ is an alkyl groupwhich may be removed by a suitable dealkylation process. Removal of suchalkyl groups from the biphenol product, if desired, is accomplishedaccording to well-known techniques. One suitable method is to heat thesubstituted biphenol at an elevated temperature below the decompositiontemperature of the biphenol. This process is described and taught inU.S. Pat. No. 4,205,187 which teaching is incorporated herein byreference. Another process particularly effective when the alkyl groupsare tertiary butyl or tertiary amyl, is to heat the alkylated biphenolin the presence of a catalytic amount of a strong acid such as p-toluenesulfonic acid. The alkyl group is effectively removed to yield therespective alkene, e.g., isobutene in the case of tertiary butyl groups,pentenes when tertiary amyl groups are employed, and the desireddealkylated biphenol product.

The isobutene or similar alkene so obtained may be recycled if desiredto alkylate phenol itself resulting in production of the substitutedphenols originally employed in the instant oxidative coupling step. Thealkylation of phenols in this manner is well-known technology. Suitably,the phenol may be readily selectively alkylated by forming first thealuminum phenoxide which is then reacted by contacting with isobutene atelevated pressure and temperature. This process is well-known havingbeen previously described in U.S. Pat. No. 2,831,898 which teaching isherein incorporated by reference.

The instant process allows for a large degree of flexibility inoperation. The catalyst may be packed into a fixed bed inside a pressurereactor. It is further possible in a continuous process to employseveral reactors, one for the oxidative coupling step and the other forthe hydrogenation. The substituted phenol is reacted in the presence ofoxygen to form diphenoquinone in the first reactor and subsequently thereaction mixture is charged to the second reactor where it is reducedpreferably by the action of hydrogen.

SPECIFIC EMBODIMENT

Having described my invention, the following examples are provided asillustrative of the invention and are not to be construed as limiting.

Example 1

In a 600-ml Parr reactor equipped with a mechanical stirrer, temperaturecontrol and gas inlet was charged 2,6-di-t-butylphenol (25 g) and 50 mlof o-dichlorobenzene. A nickel catalyst, Harshaw Ni-0104 containing 60percent nickel on Kieselguhr with a ratio of reduced nickel to totalnickel of 0.60 (2.5 g) was added along with a small amount (0.5 g) ofsodium carbonate to prevent isomerization of the reactant.

The reactor and contents were pressurized with oxygen gas to 250 psi andheated to 160° C. for 2 hours. Afterwards the reactor was vented and thecontents removed for analysis by gas-liquid chromatography according toaccepted techniques of chemical analysis. The desired product3,3',5,5'-tetra-t-butyldiphenoquinone was present in 41 percent yield.Unreacted 2,6-di-t-butylphenol comprised 29 percent of the reactionmixture.

What is claimed is:
 1. A process for preparing by an oxidation couplingreaction a carbon-carbon coupled condensation product of a substitutedphenol of the formula ##STR2## wherein each R is hydrogen, halogen orR₁, and each R₁ is a substituent having up to 10 carbons selected fromthe group consisting of hydrocarbon, halohydrocarbon and hydrocarbonoxycomprising contacting the substituted phenol with an oxygen-containinggas in the presence of a heterogeneous dehydrogenation catalystcomprising nickel in an oxidation state suitable for formingcarbon-carbon oxidatively coupled reaction products.
 2. A processaccording to claim 1 wherein the substituted phenol is a 2,6-dialkylphenol.
 3. A process according to claim 2 wherein the substituted phenolis 2,6-ditertiary butyl phenol.
 4. A process according to claim 1wherein the catalyst comprises an oxide of nickel.
 5. A processaccording to claim 3 wherein the catalyst is supported by an inertsupportive means.
 6. A process according to claim 4 wherein the inertsupport means is alumina, carbon, silica, diatomaceous earth or clay. 7.A process according to claim 1 wherein an inert liquid reaction mediumis also present.
 8. A process according to claim 7 wherein the inertliquid reaction medium is a polar compound.
 9. A process according toclaim 8 wherein the inert liquid reaction medium is methanol.
 10. Aprocess according to claim 1 which is conducted at a temperature fromabout 30° C. to about 200° C. and at an elevated pressure of up to about500 psig.
 11. The process according to claim 1 wherein the substituteddiphenoquinone is thereafter reduced.
 12. The process according to claim11 wherein the reduction is accomplished by contacting the substituteddiphenoquinone with hydrogen-containing gas in the presence of aheterogeneous hydrogenation catalyst at a temperature from about 25° C.to about 150° C. and pressures from about atmospheric to about 100 psig.